CN105885354A - Preparing method of polyhedral oligomeric silsesquioxane modified carbon nano tubes and application - Google Patents
Preparing method of polyhedral oligomeric silsesquioxane modified carbon nano tubes and application Download PDFInfo
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Abstract
The invention relates to the technical field of carbon nano tube modification, and provides a preparing method of polyhedral oligomeric silsesquioxane modified carbon nano tubes and application thereof to epoxy resin. The preparing method includes the following steps that carboxylic carbon nano tubes are preprocessed, a mixed solution of dopamine hydrochloride and the carboxylic carbon nano tubes is prepared, stirred in an ice-water bath away from light, mechanically stirred, centrifuged and purified to obtain polydopamine modified carbon nano tubes; finally the polydopamine modified carbon nano tubes and aminated polyhedral oligomeric silsesquioxane are added into organic solvent, the pH value is adjusted after mixing, after reaction is carried out at the temperature of 90-110 DEG C, the product is filtered, washed and dried to obtain the polyhedral oligomeric silsesquioxane modified carbon nano tubes. The operation method is simple and easy to implement, dispersity of the carbon nano tubes in epoxy resin and interference bonding performance can be improved, and mechanical properties and heat resistance of epoxy resin are effectively improved.
Description
Technical field
The invention belongs to carbon nano-tube modification technical field, particularly relate to preparation method and the application in the epoxy thereof of a kind of novel cage-type silsesquioxane modified carbon nano-tube.
Background technology
Nano composite material because of the combination property of its excellence, particularly its structure designability, have been widely used for the fields such as Aero-Space, energy traffic, electronic apparatus；Wherein, Epoxy-Nanocomposites is then one of material system of very attractive and application prospect.
CNT, is called for short CNTs, because of its perfect structure and the most potential application, the most always study hotspot in materialogy field.CNTs has an outstanding mechanical performance, and has excellent electricity, hot property so that it is have huge application prospect in field of compound material.CNT, by mechanism such as bridging, crack deflection, carrying internal stress, adds the performances such as the composite material strength after epoxy resin-base, toughness and is obviously improved.But, draw ratio, surface area that CNT is big cause it easily to reunite in resin matrix；And hydrophobic carbonization structure makes it relatively low with the Interface adhesive strength of resin matrix, this all have impact on the reinforced effects of CNT.Because by various physics, chemical means modified carbon nano-tube, solve its dispersion in resin and interface cohesion problem is always the study hotspot in terms of CNT reinforced epoxy composite.
Cage-type silsesquioxane, referred to as POSS, be a kind of with the organic-inorganic hybrid material between SiO2 and silicones (R2SiO) n, and to have Si-O-Si nanocage structure as core, periphery is organic group.These features make POSS have the dielectric properties of excellence, thermostability and mechanical property.POSS be used in hybrid material synthesis and preparation in be current polymer nano-scale unit hybrid material research a focus.At present, the preparation method of polymer/POSS composite mainly has two kinds: chemical copolymerization and physical blending.Chemical copolymerization method is different according to POSS Shang Suodai functional group, and it can participate in polymeric system as main chain, side chain or crosslinking points, but preparation process is relatively complicated, and structure comparison difficulty controls.Physical blending is the most simpler easy, and is not limited by POSS kind and polymer monomer polymerization methods, but the dispersion how obtaining Nano grade is the problem restricting its performance equally.In POSS chemical copolymerization or blended addition epoxy resin, the dielectric properties of epoxy resin, heat stability, impact flexibility can be significantly improved.But, along with the lifting day by day of the demand to material property, single material tends not to meet people's requirement.There is document to report, by radical polymerization, acrylate-based for prestox POSS monomer formed on CNTs surface the controlled nucleocapsid structure of clad, and join in Kynoar PVDF, it is achieved the controllable adjustment of composite dielectric properties.
Since dopamine chemistry comes out, because it is the most controlled, mild condition, superpower binding ability, it is widely used and has modified in the surface of various types of materials, especially inert material, and obtained extensive progress.Although, the mechanism of polymerization about dopamine is still not clear at present, but shows no sign of the research enthusiasm of influence research personnel.Dopamine can occur to aoxidize auto polymerization under the conditions of PH=8.5 and generate poly-dopamine, the surface being attached to material that poly-dopaminergic is firm, the CNT of dopamine modification shows good dispersibility in water, organic solvent, and poly-DOPA amine layer surface has substantial amounts of catechol group and a small amount of amino, this also provides reaction site for secondary response.
Summary of the invention
The invention provides the preparation method of a kind of cage-type silsesquioxane modified carbon nano-tube, described preparation method comprises the steps:
A, EtOH Sonicate process the carboxylic carbon nano-tube of uniform particle sizes；
B, will process after carboxylic carbon nano-tube and dopamine hydrochloride dissolve in successively in the Tris buffer of pH=8.5, carboxylic carbon nano-tube content is 0.1 ~ 1.0g/100ml, and supersound process 5 minutes under conditions of 60W-120W, obtains mixed solution I；
C, being added by dopamine hydrochloride in mixed solution I, be configured to, with mixed solution I, the mixed solution that dopamine hydrochloride concentration is 1.0 ~ 10.0g/L, lucifuge stirs in ice-water bath and is completely dissolved to dopamine hydrochloride, obtains mixed solution II；
D, mixed solution II is placed in the water bath with thermostatic control mechanical agitation 24 ~ 72 hours of 25 DEG C, obtains the mixed solution containing poly-dopamine modified lithium CNT；
E, will be containing poly-dopamine modified lithium CNT mixed solution adds deionized water, under conditions of revolution is 1000 ~ 8000 turns centrifugal 5 ~ 10 minutes, and lyophilization, obtain poly-dopamine modified lithium CNT；
F, poly-dopamine modified lithium CNT is added in organic solvent, prepare poly-dopamine modified lithium CNT: the mixed solution IV of organic solvent (m/V)=1.0 ~ 5.0g/L；
G, amination cage-type silsesquioxane is added in the organic solvent described in step f, prepare amination cage-type silsesquioxane: the mixed solution V of organic solvent (m/V)=2.0 ~ 10.0g/L；
H, mixed solution IV and mixed solution V are mixed according to the ratio of 1:1 ~ 1:5, and regulate its pH value between 8 ~ 10 with Tris buffer, obtain mixed solution VI；
I, being reacted 5 ~ 12 hours under conditions of temperature 90 ~ 110 DEG C by mixed solution VI, reaction is filtered with filter membrane after terminating, and the filtering residue obtained with toluene, ethanol, deionized water wash, is dried, obtains cage-type silsesquioxane modified carbon nano-tube successively.
Further: in described step e, lyophilization is particularly as follows: lyophilization 24 ~ 72 hours under conditions of-65 ~-55 DEG C.
Further, in described step i, membrane filtration is particularly as follows: with the membrane filtration that aperture is 0.22 μm-0.45 μm, the material of described filter membrane includes nylon, politef.
Further, described organic solvent includes: toluene, chloroform, oxolane.
Further, described churned mechanically rotating speed is 80 ~ 140r/min.
Simultaneously, present invention also offers the application of a kind of cage-type silsesquioxane modified carbon nano-tube, particularly as follows: join in epoxy resin by described cage-type silsesquioxane modified carbon nano-tube, obtain the application of cage-type silsesquioxane modified carbon nano-tube/epoxy resin composite material that novel mechanics strengthens.
Further, the addition of described cage-type silsesquioxane modified carbon nano-tube is 0.1 ~ 1.5%.
Beneficial effect
Compared with prior art, the invention has the beneficial effects as follows:
Present invention improves over the process means of original dopamine enveloped carbon nanometer tube, have chosen carboxylic carbon nano-tube, carboxyl on carboxylic carbon nano-tube first reacts with dopamine, auto polymerization occurs the most again, and chemical bond makes poly-DOPA amine layer be combined tightr with CNT with physics π-πconjugation.First CNT is sieved, it is ensured that the uniformity of CNT particle diameter is more beneficial for follow-up reaction.Centrifugal, the use of freezing dry process, can ensure that CNTs-PDA keeps the one less feed status of entanglement as far as possible.Poly-dopamine as the effective surface modifying species of one, can improve its dispersibility in the epoxy and interface cohesion.
Secondly, the present invention make use of cleverly the catechol group in poly-DOPA amine layer as secondary response site, by amination cage-type silsesquioxane (POSS-NH2) utilize schiff base reaction to be grafted on CNTs-PDA, it is prepared for POSS modified carbon nano-tube hybrid material CNTs-PDA-POSS.This material be not only two kinds are had been found to effective surface modifier dopamine, POSS is ingenious is attached on CNT；The present invention constructs a kind of novel multi-vitamin degree three-decker simultaneously, and its structure is as shown in Figure 3.The one-dimensional rigid structure of CNT, the polymer soft formation of poly-dopamine, nanoscale caged rigidity POSS of local distribution.Compare and CNTs POSS nucleocapsid structure before, this various dimensions multi-layer nano structure, it is possible to realize more effective mechanical interlock with matrix, it is achieved effective transmission of stress, be finally reached being obviously improved of mechanical performance.
And, the structure of various dimensions has effectively intercepted the π-π stacking between CNT and has also contributed to the raising of dispersibility.Unreacted catechol group can participate in the cross-linking and curing reaction of resin, and POSS also can improve the heat stability of matrix.
Finally, dopamine hydrochloride biomimetic modification CNT, it is to avoid the shortcoming such as environmental pollution that traditional method modified carbon nano-tube causes and destroying carbon nanometer tube tube wall.The firm poly-DOPA amine layer of carbon nano tube surface has good affinity and reactivity, both can improve resin compatible, catalyzed epoxies curing reaction process, and can become again the avtive spot of secondary response.
The novel multi-vitamin degree nano-hybrid material obtained after cage-type silsesquioxane modified carbon nano-tube, can improve CNT dispersibility in the epoxy and interfacial combined function, thus more effectively improve mechanical property and the thermostability of epoxy resin.
Accompanying drawing explanation
Fig. 1 is carboxylic carbon nano-tube, poly-dopamine modified lithium CNT, cage-type silsesquioxane modified carbon nano-tube fourier transform infrared spectrum comparison diagram;
Fig. 2 is carboxylic carbon nano-tube, poly-dopamine modified lithium CNT, cage-type silsesquioxane modified carbon nano-tube high resolution transmission electron microscopy comparison diagram.
Fig. 3 is that carboxylic carbon nano-tube, cage-type silsesquioxane modified carbon nano-tube are dispersed in profile scanning Electronic Speculum figure in resin matrix.
Detailed description of the invention.
Being further elucidated with the present invention, non-specified otherwise below in conjunction with being embodied as example, the reagent in embodiment is analytical pure.
Embodiment 1:
In the present embodiment, carboxylic carbon nano-tube used is bought in Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, and amination cage-type silsesquioxane used is bought in Hybrid Plastics company of the U.S.；
Step I: the carboxylic carbon nano-tube of purchase is put into sifted and separately wins the carboxylic carbon nano-tube taking 100 mesh uniform gradings, use ethanol water bath ultrasonic 1 ~ 2 hour, and dry, it is thus achieved that the CNT that uniform particle sizes, state are fluffy, named: the carboxylic carbon nano-tube that state is fluffy；
Step II: the Tris buffer that carboxylic carbon nano-tube addition PH is 8.5 that state is fluffy, is configured to the mixed solution I that carboxylic carbon nano-tube content is 0.5g/100ml, supersound process 5 minutes under conditions of 60W-120W;
Step III: added by dopamine hydrochloride in mixed solution I, is configured to the mixed solution II of the final concentration of 2.0g/L of dopamine hydrochloride with mixed solution I, and the stirring of lucifuge ice-water bath is dissolved to it.25 DEG C of water bath with thermostatic control mechanical agitation obtain the mixed solution of poly-dopamine CNT, wherein, mechanical agitation rotating speed 110r/min for 24 hours；
Step IV: by above-mentioned containing adding deionized water in poly-dopamine modified lithium CNT mixed solution, be centrifuged 5 minutes under conditions of revolution is 4000 turns, lyophilization 48 hours, obtain poly-dopamine modified lithium CNT；
Step V: poly-dopamine modified lithium CNT is added in toluene, is configured to the mixed solution IV that poly-dopamine modified lithium carbon nanotube concentration is 2g/L；
Step VI: amination cage-type silsesquioxane is added in toluene, is configured to the mixed solution V that amination cage-type silsesquioxane concentration is 2g/L；
Step VII: mixed solution IV and mixed solution V are mixed according to the ratio of 1:2, regulates its pH value with Tris buffer and obtain mixed solution VI to alkalescence 8.5；
Step VIII: react 6 hours under conditions of temperature 90 DEG C, after reaction terminates, filters with the nylon leaching film that aperture is 0.22 μm-0.45 μm, filtering residue is successively with toluene, ethanol, deionized water wash, at 50 DEG C, it is vacuum dried under conditions of 20MPa, obtains cage-type silsesquioxane modified carbon nano-tube.
Applicant have purchased traditional carboxylic carbon nano-tube and self-control poly-dopamine modified lithium CNT, and the cage-type silsesquioxane modified carbon nano-tube obtained with the present embodiment contrasts.It the results are shown in Table 1 and Figure of description:
Table 1 carboxylic carbon nano-tube, poly-dopamine are carbon nano-tube modified, POSS modifies various dimensions carbon nano-tube x-ray photoelectron spectroscopy contrast table
Table 1 shows, the silicone content of cage-type silsesquioxane modified carbon nano-tube significantly rises to 5.26%, and contrast two kinds of CNTs all can not detect silicon, it was demonstrated that cage-type silsesquioxane successfully connects CNT.
Fig. 1 is carboxylic carbon nano-tube, poly-dopamine modified lithium CNT, cage-type silsesquioxane modified carbon nano-tube fourier transform infrared spectrum comparison diagram, in figure, what uppermost curve represented is cage-type silsesquioxane modified carbon nano-tube, middle curve is poly-dopamine modified lithium CNT, and nethermost curve is carboxylic carbon nano-tube.
From the curve of Fig. 1 it is observed that at 1109cm-1The absorbing wavelength of place's Si-O-Si group, in conjunction with the data analysis of table 1, it was demonstrated that the method for the present invention can make the cage-type silsesquioxane successfully connect CNT.
Fig. 2 is carboxylic carbon nano-tube, poly-dopamine modified lithium CNT, cage-type silsesquioxane modified carbon nano-tube high resolution transmission electron microscopy comparison diagram, wherein Fig. 2 a is carboxylic carbon nano-tube, Fig. 2 b is poly-dopamine modified lithium CNT, and Fig. 2 c is cage-type silsesquioxane modified carbon nano-tube.
Can be seen that from Fig. 2 a, carboxylic carbon nano-tube has smooth sidewall, can be seen that from Fig. 2 b, after dopamine is modified, the poly-dopamine decorative layer of one layer of uniform about 3nm occurs in poly-dopamine modified lithium carbon nano tube surface, because the existence of decorative layer, the profile of poly-dopamine modified lithium CNT also thickens.From Fig. 2 c it can be seen that the present invention propose method by cage-type silsesquioxane after schiff base reaction is grafted to poly-DOPA amine layer, define the structure of a kind of various dimensions.Innermost layer is CNT, and centre is the transition zone of poly-dopamine, and outermost layer is cage-type silsesquioxane.Because the quinoid structure content that schiff base reaction can occur is different, there will be the enrichment region of cage-type silsesquioxane in some position.This various dimensions structure can transmit stress effectively, it is achieved getting a promotion of the mechanical property of the cage-type silsesquioxane modified carbon nano-tube that the present invention obtains.
Embodiment 2
In the present embodiment, carboxylic carbon nano-tube used is bought in Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, and amination cage-type silsesquioxane used is bought in Hybrid Plastics company of the U.S.；
Step I: the carboxylic carbon nano-tube of purchase is put into sifted and separately wins the carboxylic carbon nano-tube taking 200 mesh uniform gradings, use ethanol water bath ultrasonic 1.5 hours, and dry, it is thus achieved that the CNT that uniform particle sizes, state are fluffy, named: the carboxylic carbon nano-tube that state is fluffy；
Step II: the Tris buffer that carboxylic carbon nano-tube addition pH is 8.5 that state is fluffy, is configured to the mixed solution I that carboxylic carbon nano-tube content is 1.0g/100ml, supersound process 5 minutes under conditions of 60W-120W;
Step III: added by dopamine hydrochloride in mixed solution I, is configured to the mixed solution II of the final concentration of 10.0g/L of dopamine hydrochloride with mixed solution I, and the stirring of lucifuge ice-water bath is completely dissolved to it.25 DEG C of water bath with thermostatic control mechanical agitation obtain the mixed solution of poly-dopamine modified lithium CNT, wherein, mechanical agitation rotating speed 80r/min for 30 hours；
Step IV: deionized water will be added in the mixed solution of above-mentioned poly-dopamine modified lithium CNT, and be centrifuged 10 minutes under conditions of revolution is 8000 turns, lyophilization 24 hours, obtain poly-dopamine modified lithium CNT；
Step V: poly-dopamine modified lithium CNT is added in chloroform, is configured to the mixed solution IV that poly-dopamine modified lithium carbon nanotube concentration is 5.0g/L;
Step VI: amination cage-type silsesquioxane is added in chloroform, is configured to the mixed solution V that amination cage-type silsesquioxane concentration is 10g/L;
Step VII: mixed solution IV and mixed solution V are mixed according to the ratio of 1:5, regulates its pH=10 with Tris buffer and obtain mixed solution VI;
Step VIII: reacted 12 hours under conditions of temperature 110 DEG C by mixed solution VI, after reaction terminates, filters with the teflon membrane filter that aperture is 0.45 μm, filtering residue is successively with toluene, ethanol, deionized water wash, at 80 DEG C, vacuum drying, obtain cage-type silsesquioxane modified carbon nano-tube.
Embodiment 3
In the present embodiment, carboxylic carbon nano-tube used is bought in Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, and amination cage-type silsesquioxane used is bought in Hybrid Plastics company of the U.S.；
Step I: the carboxylic carbon nano-tube of purchase is put into sifted and separately wins the carboxylic carbon nano-tube taking 300 mesh uniform gradings, use ethanol water bath ultrasonic 2 hours, and dry, it is thus achieved that the CNT that uniform particle sizes, state are fluffy, named: the carboxylic carbon nano-tube that state is fluffy；
Step II: the Tris buffer that carboxylic carbon nano-tube addition pH is 8.6 that state is fluffy, is configured to the mixed solution I that carboxylic carbon nano-tube content is 0.1g/100ml, supersound process 5 minutes under conditions of 120W;
Step III: added by dopamine hydrochloride in mixed solution I, is configured to the mixed solution II of the final concentration of 1.0g/L of dopamine hydrochloride with mixed solution I, and the stirring of lucifuge ice-water bath is to dissolving.25 DEG C of water bath with thermostatic control mechanical agitation obtain the mixed solution of poly-dopamine modified lithium CNT, wherein, mechanical agitation rotating speed 140r/min for 72 hours；
Step IV: deionized water will be added in the above-mentioned mixed solution containing poly-dopamine modified lithium CNT, and be centrifuged 5 minutes under conditions of revolution is 1000 turns, lyophilization 72 hours, obtain the poly-dopamine modified lithium CNT of purification；
Step V: poly-dopamine modified lithium CNT is added in oxolane, is configured to the mixed solution IV that poly-dopamine modified lithium carbon nanotube concentration is 1.0g/L;
Step VI: amination cage-type silsesquioxane is added in oxolane, is configured to the mixed solution V that amination cage-type silsesquioxane concentration is 4g/L;
Step VII: mixed solution IV and mixed solution V are mixed according to the ratio of 1:1, regulates its pH=10 with Tris buffer and obtain mixed solution VI;
Step VIII: reacted 5 hours under conditions of temperature 100 DEG C by mixed solution VI, after reaction terminates, filters with the teflon membrane filter that aperture is 0.22 μm, filtering residue is successively with toluene, ethanol, deionized water wash, at 60 DEG C, vacuum drying, obtain cage-type silsesquioxane modified carbon nano-tube.
Embodiment 4
Being added in epoxy resin by prepared cage-type silsesquioxane modified carbon nano-tube, wherein, the addition of cage-type silsesquioxane modified carbon nano-tube is 0.5 ~ 1.5%.Use conventional ultrasound, churned mechanically method, add DDM firming agent, obtain carboxylic carbon nano-tube/epoxy resin composite material.
Fig. 3 a is the scanning electron microscope diagram at carboxylic carbon nano-tube/epoxy resin composite material destruction prepared by the present embodiment, Fig. 3 b be cage-type silsesquioxane various dimensions carbon nano-tube modified/scanning electron microscope diagram of epoxy resin composite material.Comparing and when being destroyed, can more effectively transmit load with the CNT of cage-type silsesquioxane various dimensions modification in Fig. 3 a, Fig. 3 b, section is more coarse, it is possible to many absorption stress, thus improves the mechanical property of material.
Claims (7)
1. the preparation method of a cage-type silsesquioxane modified carbon nano-tube, it is characterised in that described preparation method comprises the steps:
A, EtOH Sonicate process the carboxylic carbon nano-tube of uniform particle sizes；
B, will process after carboxylic carbon nano-tube and dopamine hydrochloride dissolve in successively in the Tris buffer of pH=8.5, carboxylic carbon nano-tube content is 0.1 ~ 1.0g/100ml, and supersound process 5 minutes under conditions of 60W-120W, obtains mixed solution I；
C, being added by dopamine hydrochloride in mixed solution I, be configured to, with mixed solution I, the mixed solution that dopamine hydrochloride concentration is 1.0 ~ 10.0g/L, lucifuge stirs in ice-water bath and is completely dissolved to dopamine hydrochloride, obtains mixed solution II；
D, mixed solution II is placed in mechanical agitation 24 ~ 72 hours under the constant temperature of 25 DEG C, obtains containing poly-dopamine modified lithium CNT mixed solution；
E, poly-dopamine modified lithium CNT mixed solution will add deionized water, under conditions of revolution is 1000 ~ 8000 turns centrifugal 5 ~ 10 minutes, and lyophilization, obtain poly-dopamine modified lithium CNT；
F, poly-dopamine modified lithium CNT is added in organic solvent, prepare poly-dopamine modified lithium CNT: the mixed solution IV of organic solvent (m/V)=1.0 ~ 5.0g/L；
G, amination cage-type silsesquioxane is added in the organic solvent described in step f, prepare amination cage-type silsesquioxane: the mixed solution V of organic solvent (m/V)=2.0 ~ 10.0g/L；
H, mixed solution IV and mixed solution V are mixed according to the ratio of 1:1 ~ 1:5, and regulate its pH value between 8 ~ 10 with Tris buffer, obtain mixed solution VI；
I, being reacted 5 ~ 12 hours under conditions of temperature 90 ~ 110 DEG C by mixed solution VI, reaction is filtered with filter membrane after terminating, and the filtering residue obtained with toluene, ethanol, deionized water wash, is dried, obtains cage-type silsesquioxane modified carbon nano-tube successively.
The preparation method of cage-type silsesquioxane modified carbon nano-tube the most according to claim 1, it is characterised in that: in described step e, lyophilization is particularly as follows: lyophilization 24 ~ 72 hours under conditions of-65 ~-55 DEG C.
The preparation method of cage-type silsesquioxane modified carbon nano-tube the most according to claim 1, it is characterised in that: in described step i, filter filter membrane used be aperture be the filter membrane of 0.22 μm-0.45 μm, the material of described filter membrane includes nylon, politef.
The preparation method of cage-type silsesquioxane modified carbon nano-tube the most according to claim 1, it is characterised in that: described organic solvent includes: toluene, chloroform, oxolane.
The preparation method of cage-type silsesquioxane modified carbon nano-tube the most according to claim 1, it is characterised in that: described churned mechanically rotating speed is 80 ~ 140r/min.
6. the application of the cage-type silsesquioxane modified carbon nano-tube described in a claim 1, it is characterized in that: described cage-type silsesquioxane modified carbon nano-tube is joined in epoxy resin, obtain cage-type silsesquioxane modified carbon nano-tube/epoxy resin composite material that novel mechanics strengthens.
The epoxy resin composite material that cage-type silsesquioxane modified carbon nano-tube the most according to claim 6 strengthens, it is characterised in that: the interpolation weight fraction of described cage-type silsesquioxane modified carbon nano-tube is 0.1 ~ 1.5%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644494A (en) * | 2004-12-22 | 2005-07-27 | 华东师范大学 | Method for preparing carbon nanometer tube composites by sol and gel method |
| CN103012806A (en) * | 2012-12-27 | 2013-04-03 | 复旦大学 | Synthetic method and application of polydopamine-modified carbon nanotube composite material |
| CN103173041A (en) * | 2013-03-08 | 2013-06-26 | 北京化工大学 | Method for making core-shell polyhedral oligomeric silsesquioxane (POSS) coated multi-walled carbon nanotube (MWNT) |
| CN104072762A (en) * | 2014-06-13 | 2014-10-01 | 西安交通大学 | Preparation method of magnetic carbon nanotube with polydopamine-modified surface |
| KR101477015B1 (en) * | 2013-12-19 | 2014-12-30 | 한국수자원공사 | Method for preparation of carbon nanotube coated with polydopamine and carbon nanotube coated with polydopamine prepared thereby |
-
2016
- 2016-06-06 CN CN201610391144.3A patent/CN105885354B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644494A (en) * | 2004-12-22 | 2005-07-27 | 华东师范大学 | Method for preparing carbon nanometer tube composites by sol and gel method |
| CN103012806A (en) * | 2012-12-27 | 2013-04-03 | 复旦大学 | Synthetic method and application of polydopamine-modified carbon nanotube composite material |
| CN103173041A (en) * | 2013-03-08 | 2013-06-26 | 北京化工大学 | Method for making core-shell polyhedral oligomeric silsesquioxane (POSS) coated multi-walled carbon nanotube (MWNT) |
| KR101477015B1 (en) * | 2013-12-19 | 2014-12-30 | 한국수자원공사 | Method for preparation of carbon nanotube coated with polydopamine and carbon nanotube coated with polydopamine prepared thereby |
| CN104072762A (en) * | 2014-06-13 | 2014-10-01 | 西安交通大学 | Preparation method of magnetic carbon nanotube with polydopamine-modified surface |
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